EP4281409A1 - Méthode de régulation de composition de gaz de synthèse par la température de réacteur - Google Patents

Méthode de régulation de composition de gaz de synthèse par la température de réacteur

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Publication number
EP4281409A1
EP4281409A1 EP21840260.0A EP21840260A EP4281409A1 EP 4281409 A1 EP4281409 A1 EP 4281409A1 EP 21840260 A EP21840260 A EP 21840260A EP 4281409 A1 EP4281409 A1 EP 4281409A1
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EP
European Patent Office
Prior art keywords
reactor
stream
partial oxidation
ratio
temperature
Prior art date
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EP21840260.0A
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German (de)
English (en)
Inventor
Bradley D. DAMSTEDT
Lawrence E. Bool
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Praxair Technology Inc
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Praxair Technology Inc
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Application filed by Praxair Technology Inc filed Critical Praxair Technology Inc
Publication of EP4281409A1 publication Critical patent/EP4281409A1/fr
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
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    • C01INORGANIC CHEMISTRY
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    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C01B2203/0216Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic steam reforming step
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/025Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0255Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0283Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0475Composition of the impurity the impurity being carbon dioxide
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0485Composition of the impurity the impurity being a sulfur compound
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/062Hydrocarbon production, e.g. Fischer-Tropsch process
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0861Methods of heating the process for making hydrogen or synthesis gas by plasma
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons
    • C01B2203/1241Natural gas or methane
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/148Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/0916Biomass
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983Additives
    • C10J2300/0989Hydrocarbons as additives to gasifying agents to improve caloric properties
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/16Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656Conversion of synthesis gas to chemicals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807Recycle loops, e.g. gas, solids, heating medium, water
    • C10J2300/1823Recycle loops, e.g. gas, solids, heating medium, water for synthesis gas
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846Partial oxidation, i.e. injection of air or oxygen only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72Other features
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology

Definitions

  • the present invention relates to the production of syngas so as to control significant characteristics of the syngas so produced.
  • a primary gasifier consists of a vessel, typically refractory lined, where a primary feed is mixed with an oxidant stream.
  • Common oxidant streams include steam, CO2, oxygen, or mixtures of these streams.
  • other species may also be included, such as N2 or Ar.
  • the ratio of oxidant to feedstock is controlled such that less oxidant is provided than required to completely combust the feedstock. This condition, termed “fuel rich”, leads to the production of desired species such as CO and H2 by partial oxidation.
  • the resulting crude syngas is typically then purified and sent to a downstream process for use. Examples of downstream processes include ethanol production and Fischer-Tropsch (“FT”) processes for liquid fuels production.
  • FT Fischer-Tropsch
  • the syngas produced by primary gasification may contain significant amounts of unreacted higher molecular weight hydrocarbons which can be problematic for downstream equipment.
  • problematic hydrocarbons are those commonly denoted as “tars” that condense in downstream equipment potentially causing operational and efficiency issues.
  • These problematic hydrocarbons can be further processed by secondary gasification of the hydrocarbon-containing syngas from a primary gasifier.
  • This configuration is similar to a primary gasifier except that the feedstock to the secondary gasifier includes, at least in part, the crude syngas from the primary gasifier.
  • a secondary gasifier may be used with feedstocks generated from hydrocarbon processing, such as refinery off gas (that is, crude syngas is not necessarily generated from a gasification process).
  • a gasification process is particularly suited for chemicals manufacturing.
  • H2 and CO are converted to chemicals using a variety of processes, including catalytic or biological reactors.
  • syngas from a gasification system is conditioned in any of several ways; a partial list of potential conditioning actions is given below.
  • Each conditioning step increases the operating complexity as well as capital and operating cost of the overall chemical plant, so plants limit the number of conditioning steps to only those required.
  • remove catalyst poisons for example HCN, sulfur containing species such as H2S or other contaminants reduce diluents, for example CO2 and H2O adjust properties, for example pressure and temperature adjust chemical composition, for example adding nutrients for biological reactors or adjusting the H2 to CO ratio using a water gas shift reactor (WGS).
  • WGS water gas shift reactor
  • H2:CO ratio of a gasification system may not fall within the range required by the downstream process.
  • the native H2:CO ratio of products formed by partial oxidation (POx) gasifiers using natural gas (“NG”) as a feedstock fall within the range of 1.7 to 1.8. If NG is being converted to syngas using a POx gasifier and the syngas is intended to be used to generate ethanol using FT processing, the H2:CO ratio of this syngas will preliminarily be adjusted upward using a WGS reactor. Because of the many types of gasifiers, feedstocks, chemical conversion processes and chemicals, it is recognized that linking the gasification process to the chemical product generation process will usually require adjustment of the H2:CO ratio.
  • Adjusting the H2:CO ratio in syngas produced by POx and other gasifiers has previously been accomplished by adding, directly into the POx reactor or into a reactant stream that is fed into the POx reactor, either H2O in the form of steam for situations where a higher H2:CO ratio is desired or a CO2 rich stream when a reduction in H2:CO ratio is desired.
  • a source of CO2 may be a CO2 stream obtained by a removal process in the conditioning steps.
  • SMR steam methane reformers
  • ATR auto thermal reformers
  • the present invention utilizes discoveries that enable the control of the characteristics of the syngas which is produced in the POx reactor, that provide advantages in being able to control the characteristics of the syngas and the operation of the plant.
  • One embodiment of the present invention is a method of producing syngas, comprising: feeding hydrocarbonaceous feedstock material and oxygen to a reactor; partially oxidizing the hydrocarbonaceous feedstock material in the reactor to produce a product stream comprising H2, CO, and hydrocarbons that leaves the reactor, wherein the partial oxidation is carried out at reaction conditions including a reaction temperature which is lower than the temperature at which partial oxidation of the feedstock material, at the same reaction conditions other than the temperature, would minimize the amount of unreacted hydrocarbons in the product stream produced by partially oxidizing the feedstock material, thereby providing H2 and CO in the product stream wherein the H2:CO ratio is higher than the value the ratio would exhibit upon partial oxidation at said reaction conditions including at a temperature higher than said reaction temperature; and recovering from the reactor a product stream comprising hydrogen and CO formed in the reactor and unreacted hydrocarbons.
  • unreacted hydrocarbon in said product stream, or products obtained by reaction of said unreacted hydrocarbon recovered from the product stream is recycled to the reactor in which the partial oxidation is performed.
  • This embodiment enhances the ability of the operator to improve overall efficiency of the plant based on the hydrocarbonaceous feedstock.
  • Figure 1 is a flowsheet of a facility that utilizes partial oxidation to produce hydrocarbon product such as fuels from feedstock.
  • Figure 2 is a cross-sectional view of a device that can produce a stream of hot oxygen useful in this invention.
  • FIGS. 3 through 8 are graphs showing characteristics of the invention. Detailed Description of the Invention
  • the present invention is particularly useful in operations that convert hydrocarbon products such as biomass to useful hydrocarbon products such as (but not limited to) liquid fuel.
  • the product produced by the present invention includes products that can be sold and used as-is, as well as products that can be used as reactants to produce other finished useful products that can then be sold and used.
  • Figure l is a flowsheet that shows the typical steps of such an operation.
  • stream 1 which is also referred to herein as the raw feedstock is fed to partial oxidation reactor 4.
  • Stream 1 is provided from source 11 which designates a production facility or reactor in which raw feed 1 is produced.
  • Suitable raw feedstocks 1 and their sources 11 include:
  • Natural gas from any commercial source thereof; the gaseous stream that is produced by a gasification reactor, in which solid hydrocarbon material such as biomass or solid fossil fuel such as coal or lignin is gasified in a stream of gas usually comprising air, steam, and/or oxygen at a high enough temperature that at least a portion of the solid material is converted to a gaseous raw stream 1; product streams and byproduct streams, which more often are gaseous but may be liquid and/or solids, that are produced in a petrochemical refinery or chemical plant; coke oven gas, being the offgas stream that is produced in a reactor that heat treats coal to produce coke; pyrolysis gas, being a hydrocarbon-containing gaseous stream that is produced in a reactor to heat treat solid carbonaceous material such as fossil fuel or biomass to devolatilize and partially oxidize the solid material;
  • a gasification reactor in which solid hydrocarbon material such as biomass or solid fossil fuel such as coal or lignin is gasified in a stream of gas usually comprising air, steam
  • feedstock streams include oils, such as pyrolysis oils, and liquid hydrocarbons.
  • Raw feedstock 1 generally contains hydrogen and carbon monoxide (CO), and typically also contains one or more hydrocarbons such as alkanes and /or alkanols of 1 to 18 carbon atoms, and often contains one or more of carbon dioxide (CO2), and higher molecular weight hydrocarbons characterized as tars and/or soot.
  • CO carbon monoxide
  • hydrocarbons such as alkanes and /or alkanols of 1 to 18 carbon atoms
  • CO2 carbon dioxide
  • tars and/or soot higher molecular weight hydrocarbons characterized as tars and/or soot.
  • Raw feedstock stream 1 is then fed into partial oxidation reactor 4 in which it is reacted (under conditions described more fully below) with oxygen that is provided as hot oxygen stream 2 (produced as more fully described below) to produce additional amounts of hydrogen and carbon monoxide (CO) from components present in stream 1. If tars are present in the stream, some or all of tars present can also be converted to lower molecular weight hydrocarbon products.
  • Steam represented as stream 12, can optionally also be added to reactor 4, as described herein.
  • Oxidized product stream 13 which is produced in partial oxidation reactor 4 is fed to stage 6 in which stream 13 is preferably cooled and treated to remove substances that should not be present when the stream is fed to reactor 10 (described hereinbelow).
  • Stage 6 typically includes a unit which cools stream 13, for instance by indirect heat exchange with incoming feed water 61 to produce stream 62 of heated water and/or steam.
  • stage 6 can also comprise a shift conversion reactor in which carbon monoxide in stream 13 is reacted (in a non-limiting example, with water vapor (steam)) in a catalytically mediated water-gas shift (“WGS”) reaction to produce hydrogen, thereby providing a way to adjust the ratio of hydrogen to carbon monoxide in stream 13.
  • WGS catalytically mediated water-gas shift
  • stage 8 The resultant stream 14, having been cooled and/or having had its hydrogen:CO ratio adjusted in stage 6, is fed to stage 8 in which impurities 81 that may be present such as particulates, acid gases including CO2, ammonia, sulfur species, and other inorganic substances such as alkali compounds, are removed. Impurities may be removed in one unit or in a series of units each intended to remove different ones of these impurities that are present or to reduce specific contaminants to the desired low levels. Stage 8 represents the impurities removal whether achieved by one unit or by more than one unit. Cooling and impurities removal are preferably performed in any effective sequence in a series of stages or all in one unit. Details are not shown but will be familiar to those skilled in the art.
  • Stage 8 typically includes operations for final removal of impurities, non-limiting examples of which include particulates, NH3, sulfur species and CO2.
  • the CO2 removal is typically performed by a solvent-based process, which either uses a physical solvent, e.g. methanol, or a chemical solvent, e.g. amine.
  • stage 10 which represents any beneficial use of one or more components present in stream 15. That is, stream 15 can be used as-is as an end product. However, the present invention is particularly useful when stream 15 is to serve as feed material for further reaction and/or other processing that produces product designated as 20 in Figure 1.
  • stream 15 is converted into liquid fuels, such as using stream 15 as feed material to a Fischer-Tropsch process or other synthetic methodology to produce a liquid hydrocarbon or a mixture of liquid hydrocarbons useful as fuel.
  • useful treatment of stream 15 include the production of specific targeted chemical compounds such as ethanol, straight-chain or branched-chain or cyclic alkanes and alkanols containing 4 to 18 carbon atoms, aromatics, and mixtures thereof; or in the production of longer-chain products such as polymers.
  • the overall composition of stream 15 can vary widely depending on the composition of raw feedstock 1, on intermediate processing steps, and on operating conditions.
  • Stream 15 typically contains (on a dry basis) 20 to 50 vol.% of hydrogen, and 10 to 45 vol.% of carbon monoxide.
  • one or more properties of stream 15 will continually exhibit a value, or a value that falls within a characteristic desired range, in order to accommodate the treatment that stream 15 is to undergo in stage 10 to produce a repeatable, reliable supply of product 20.
  • the property of stream 15 that is relevant and that should be maintained within a desired ratio is the molar ratio of hydrogen (H2) to CO.
  • H2 hydrogen
  • the target range of Fh CO molar ratio depends on the product being produced. For example, ethanol production is most efficient with H2:CO within the range of 1.95 to 2.05. Synthetic gasoline production requires a F CO ratio in the range of 0.55 to 0.65.
  • the target range of H2:CO molar ratio can be very large.
  • processing in stage 10 may produce byproduct stream 26, which can be recycled to partial oxidation reactor 4 to be used as a reactant, and/or recycled to hot oxygen generator 202 (described below with respect to Figure 2) to be combusted in hot oxygen generator 202 as described herein.
  • Steam (stream 62) formed from water stream 61 in stage 6 can be optionally fed to partial oxidation reactor 4.
  • hot oxygen stream 2 is fed to partial oxidation reactor 4 to provide oxygen for the desired partial oxidation of raw feedstock 1, and to provide enhanced mixing, accelerated oxidation kinetics, and accelerated kinetics of the reforming with reactor 4.
  • the desired high temperature, high velocity oxygencontaining stream can be provided, such as plasma heating.
  • hot oxygen generator 202 that can provide hot oxygen stream 2 at a high velocity.
  • Stream 203 of gaseous oxidant preferably having an oxygen concentration of at least 30 volume percent and more preferably at least 85 volume percent is fed into hot oxygen generator 202 which is preferably a chamber or duct having an inlet 204 for the oxidant 203 and having an outlet nozzle 206 for the stream 2 of hot oxygen.
  • the oxidant 203 is technically pure oxygen having an oxygen concentration of at least 99.5 volume percent.
  • the oxidant 203 fed to the hot oxygen generator 202 has an initial velocity which is generally within the range of from 50 to 300 feet per second (fps) and typically will be less than 200 fps.
  • Stream 205 of fuel is provided into the hot oxygen generator 202 through a suitable fuel conduit 207 ending with nozzle 208 which may be any suitable nozzle generally used for fuel injection.
  • the fuel may be any suitable combustible fluid examples of which include natural gas, methane, propane, hydrogen and coke oven gas, or may be a process stream such as stream 26 obtained from stage 10.
  • the fuel 205 is a gaseous fuel. Liquid fuels such as number 2 fuel oil or byproduct stream 23 may also be used.
  • the fuel in stream 205 and the oxidant stream 203 should be fed into generator 202 at rates relative to each other such that the amount of oxygen in oxidant stream 203 constitutes a sufficient amount of oxygen for the intended use of the hot oxygen stream.
  • the fuel 205 provided into the hot oxygen generator 202 combusts therein with oxygen from oxidant stream 203 to produce heat and combustion reaction products which may also include carbon monoxide.
  • the combustion within generator 202 generally raises the temperature of remaining oxygen within generator 202 by at least about 500°F, and preferably by at least about 1000°F.
  • the hot oxygen obtained in this way is passed from the hot oxygen generator 202 as stream 2 into partial oxidation reactor 4 through and out of a suitable opening or nozzle 206 as a high velocity hot oxygen stream having a temperature of at least 2000°F up to 4700°F.
  • the velocity of the hot oxygen stream 2 as it passes out of nozzle 206 will be within the range of from 500 to 4500 feet per second (fps), and will typically exceed the velocity of stream 203 by at least 300 fps.
  • the momentums of the hot oxygen stream and of the feedstock should be sufficiently high to achieve desired levels of mixing of the oxygen and the feed.
  • the momentum flux ratio of the hot oxygen stream to the feedstock stream should be at least 3.0.
  • composition of the hot oxygen stream depends on the conditions under which the stream is generated, but preferably it contains at least 50 vol.% O2 and more preferably at least 65 vol.% O2.
  • the formation of the high velocity hot oxygen stream can be carried out in accordance with the description in U.S. Patent No. 5,266,024.
  • the characteristics of the product to be formed in stage 20 are required to change, necessitating a change on the H2:CO ratio of the syngas at 13.
  • the characteristics of raw feedstock 1 that could change include the total hydrocarbon concentration of the raw feed; the total concentration of C2H2, C2H4, and tars; and the temperature. Examples of circumstances that could cause any of these characteristics to change include:
  • the composition of raw feedstock 1 has changed because the feed to source 11 has changed.
  • the raw feedstock 1 from its source 11 has become too expensive relative to other compositions, from other sources, that could be useful feedstock material to the POx reactor 4.
  • the treatment provided in one or more of the stages 6 and 8 has changed, such as changes to the catalytic processing that is provided in the WGS reaction.
  • the injector system that feeds material into the POx reactor has been damaged or fouled so that the ability of the feedstock material to be entrained into the hot oxygen stream is lessened, thereby leading to excessive methane slip, excessive tar slip, and/or excessive soot formation.
  • the present invention enables the operator several advantages: the ability to adjust the H2:CO ratio of the syngas product that emerges from the POx reactor, to compensate for any changes in the overall operation that would require adjustment of the H2:CO ratio of that product; and the ability to improve the overall efficiency of utilization of the feedstock material.
  • One advantage of this invention is the ability to affect the H2:CO ratio of the product stream 13. This is confirmed in Example 1.
  • Example 1 syngas generated by reacting ambient temperature CH4 with hot oxygen generated through the use of a thermal nozzle as described herein with reference to Figure 2.
  • the reactor pressure is assumed to be 115 psig and the reactor is assumed to be adiabatic.
  • a previously validated kinetic model was used to estimate syngas production after 4 seconds residence time. Results from the prediction are shown in Figure 3, plotted as a function of reactor temperature. Yield is given as the combined amount of (H2 + CO) divided by the total amount of CH4 used, shown as the curve in squares. CH4 slip is shown as the curve in diamonds and the H2:CO ratio is shown as the curve in triangles.
  • the reactor temperature will be held to a value that ensures the hydrocarbon slip never exceeds the desired value but no higher. Any unreacted hydrocarbon leaving the gasifier is removed during downstream processing and either purged and sent to a flare, or is used in a lower value method (fuel value).
  • the gasifier whether primary or secondary, is operated counter to conventional wisdom such that the hydrocarbon slip is increased.
  • the gasifier is operated at a lower temperature, which would yield a lower single pass efficiency.
  • less of the hydrocarbon that is consumed ends up as complete combustion products (CO2 and H2O). This means the amount of CO and H2 produced per unit of hydrocarbon consumed is increased. If the unreacted hydrocarbons are recycled to the gasifier after separation from the syngas (or from products derived from the syngas) the overall hydrocarbon yield can be increased per amount of fresh feed.
  • This invention is particularly valuable if the carbon and hydrogen atoms in the feedstock have value above simple fuel value.
  • the carbon and hydrogen atoms in the feedstock are from renewable sources, then the final products derived from these renewable sources, such as a transportation fuel, may have a much higher value than if those same carbon and hydrogen molecules are simply flared or used as a fuel.
  • the hydrocarbon feedstock is more expensive than a conventional feedstock it is desirable to convert more of the hydrocarbon feedstock to final product.
  • a crude syngas generated from an upstream hydrocarbon processing unit is reacted in a secondary gasifier.
  • the oxidant is hot oxygen generated through the use of a thermal nozzle as described herein with reference to Figure 2.
  • Compositions for the crude feedstock, fuel to the thermal nozzle, and oxygen to the thermal nozzle are shown in Table 1.
  • none of the supplies are assumed to be preheated (i.e.; feedstock to the gasifier, fuel and oxygen to the thermal nozzle, are all assumed to be at ambient temperature).
  • the reactor pressure is assumed to be 50 psig and the reactor is assumed to be adiabatic.
  • a previously validated kinetic model was used to estimate the syngas production after 4 seconds residence time.
  • the peak bulk conversion efficiency takes place at a reactor temperature of approximately 2530 °F. However, operating at a lower temperature of approximately 2450 °F yields an increase in the hydrocarbon conversion efficiency of approximately 1%.
  • pure ambient temperature methane is fed to a primary gasifier where it is mixed with the effluent of a thermal nozzle that produced hot oxygen from a mixture of ambient temperature pure methane and ambient temperature pure oxygen.
  • the gasifier is assumed to be adiabatic and operate at 115 psig.
  • the validated kinetic model was used to estimate the syngas characteristics from the reactor at 4 seconds residence time. The results of the kinetic calculations are shown in Figure 8. When the gasifier is operated in single pass mode, consistent with normal gasifier operation, the peak conversion of the total fresh methane fed to the reactor (feed and thermal nozzle fuel) is found at approximately 2660 °F.

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  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
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  • Hydrogen, Water And Hydrids (AREA)
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Abstract

L'invention concerne une méthodologie de régulation du rapport H2:CO du produit produit dans un réacteur d'oxydation partielle, par réalisation de l'oxydation partielle dans des conditions de température qui produisent moins que la conversion maximale.
EP21840260.0A 2021-01-25 2021-12-08 Méthode de régulation de composition de gaz de synthèse par la température de réacteur Pending EP4281409A1 (fr)

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US5266024A (en) 1992-09-28 1993-11-30 Praxair Technology, Inc. Thermal nozzle combustion method
US20120023822A1 (en) * 2010-07-29 2012-02-02 Air Products And Chemicals, Inc. Method and System for Controlled Gasification
US20170320730A1 (en) * 2014-10-27 2017-11-09 Aghaddin Mamedov Integration of syngas production from steam reforming and dry reforming
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